Photographic film



Patented oei. 12, 1943 f UNITED STATES PHOTOGRAPHIC FILM Gale E. Nadeau and Clemens B. stai-ek, mehester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application November 26, 1940, Serial No. 367,178

14 claims.

'I'his invention relates to a method for subbing photographic film and particularly to asub for filmV designed to receive a colored photo- .graphic image.

The problem of producing a satisfactory safety lm base possessing satisfactory stripping and brittleness qualities has been extremely diillcult to solve. In order to4 cause photographic emulsion layers to adhere to cellulose organic'acid ester supports, it is .necessary to use-intervening layers of such a character that the several layers do not strip from the support when the iilmA is used or when the film is passed through processing baths, and also of such character that the layers do not adhere with such firmness that the film becomes brittle. One successful way of making a photographic film having satisfactory stripping and brittleness is to use a synthetic resinous material as a sub or undercoat as described in Nadeau UfS. Patent 2,133,110 granted October 11, 1938. The problem of causing a photographic emulsion to adhere to cellulose inorganic acid ester supports such as cellulose nitrate is not difficult, since it is necessary only to employ a simple gelatin sub on the cellulose nitrate support and overcoat with the usual gelatino-silver halide emulsion.

In the case of photographic iilm having an emulsion layer or several emulsion layers sensitized to record different regions ofthe spectrum and designed to receive colored images the subbingor undercoat layers must possess additional qualities. The dye or other coloring material used in the emulsion layers is likely to stain the sub coat if it is'not properly constructed and the sub coat may cause a fading of the dye in the emulsion'layer of the lm nextto the sub, when the film is incubated or stored. One method of preventing the retention of dye in a sub coat consists of using for this coating a mixture of a cellulose ester and a resin as described in a prior patent, Nadeau U. S. 2,169,004, granted A August 8, 1939. Other methods which might appear to alleviate the condition of dye retention in subbing layers involve the use of mixed gelatin and synthetic resin subbing layers, as described in the prior U. S. patents, Babcock 2,096,675, Nadeau' 2,096,616 and 2,096,617,- all granted October 19, 1937. These methods, .while 50 representing jan approach in the right direction do not entirely solve-the problem inasmuch as some dyes tend to be retained in subblng layers, 'constructed according to the prior art, after processing a color film by well known methods. In addition it has been determined that films subbed with layers of material either containing an aldehyde or a material capable of decomposition into an aldehyde will show significantly high fog upon development.

The object f lthe present invention is to pro.

vide a subbing layer for a photographic nlm having an emulsion layer or layers designed to receive colored images, vwhich does not retain a dye stain caused by the colored image or dyes present inthe iilm or formed during color processing operations. A further object is to provide a subbing layer which imparts satisfactory physical properties to a film. A still further object is to provide a photographic lm with a subbing layer which is free of fog-producing substances.

These objects are accomplished in the present invention by providing a subbing layer consisting of a mixture of gelatin and a polymeric material, such as a polyvinyl ester, free from aldehyde or aldehyde-forming substances.

In the accompanying drawing Figs. 1, 2, 3 and 4 are enlarged sectional views of a photographic film having subbing layers thereon according to our invention.

` In subbing iilm according to our invention a cellulose derivative support is coated with a sub-v bing layer of gelatinv and a polyvinyl ester. The

support may consist of celluloseorganic acid esters and mixed esters such as cellulose acetate or acetate propionate and cellulose inorganic acid esters vsuch as cellulose nitrate. The polyvinyl ester of the subbing layer may be a fully esterifled lester such as polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate or a partially hydrolyzed polyvinyl ester. These polyvinyl esters are prepared by the esterication of polyvinyl alcohol, although it is questionable whether completely 'esteried polyvinyl esters are produced by this method. Otherwise a monomeric vinyl ester is polymerized to the polyvinyl ester and from this by hydrolysis may be prepared a partially hydrolyzed polyvinyl ester. The polyvinyl acetate we generally use is known under the trade trade "Gelva, the preparation of which is described in U. S. patents, Klatte and Rollett 1,241,738, granted October 2, 1917; Herrmann et al. 1,586,803, granted June 1, 1926, and 1,710,-

825, granted April 30, 1929. We prefer to use the lower viscosity polymers prepared by these methods known as Gelva V-15, V-25 or Vy-30. Other resins which are suitable for use in the subbing layers of our invention in conjunction with gelatin but which are not generally as effective in the reduction of dye stain, are -polyvinyl formaldehyde and acetaldehyde acetals and the esters of polyacrylic acid. After the application of the snbbing layer of our invention to a support the sensitive emulsion layer or layersare coated thereupon usually without the interposition ofany intervening adhesive layers. We prefer, however. in the case of mixed cellulose organicacid ester supports, rst to sub the support with a hydrolyzed cellulose ester layer or,

and polyvinyl ester layer, then the gelatin and polyvinyl ester layer, and iinally the emulsion. -V

Cellulose nitrate and cellulose .acetate supports may be subbed by an alternative method. We first coat the support with a cellulose nitrate or mixed cellulose nitrate and l 0lyvinyl acetate.

layer followed by the mixed gelatin and polyvinyl ester subbing layer of our invention and one or more emulsion layers.

Our invention will now be described by particular reference to the accompanying drawing.

As shown in Fig. 1 a cellulose ester support I Il is subbed with a mixture ofvgelatin and a polymeric material free from aldehyde, e. g., gelatin and polyvinyl ester layer I'I. The emulsion layer I2 is coated over the subbing layer II.

As shown in Fig. 2 a cellulose nitrate support III is subbed with a mixed gelatin and polyvinyl acetate layer II and over this layer is coated the f emulsion layer I2.

As shown in Fig. 3 a cellulose acetate support I is subbed with cellulose nitrate or mixed cellulose nitrate and polyvinyl acetate layer I3 followed by the mixedgelatln and polyvinyl acetate subbing layer II' and the emulsion layer I2.

As shown in Fig. 4 a color illm sensitized to record diiferent regions of the spectrum consists of a cellulose acetate propionate. support i0 and in order thereupon a cellulose nitrate or mixed cellulose nitrate and polyvinyl acetate layer I3,

the mixed gelatin and polyvinyl acetate layer I I, and the red, green, and blue light sensitive emulsion layers I5, Il and I1.

The methodof subbing nlm according -to our invention will now be illustrated by examples, it being understood that these are illustrative only.

Emmple 1 A cellulose nitrate nlm support was coated .with the following subbing solution to which had been Over this layer was coated an ordinary emulsion layer. This film had satisfactory physical characteristics such as flexibility without brittleness and when\a colored image was formed inthe emulsion layer the subbing layer did not retain any dye. V

Example 2 A cellulose nitrate' film support was coated with the following subbing solution. e

' Per cent Cellulose nitrate (80-90% soluble in alcohol,

low viscosity, 11% N) 2.5 Polyvinyl acetate 0.6 Acetone 35.0 Methanol 56.9 Butyl alcnhni 5 0 This solution was coated at a linear speed of 6 ieet per minute and was dried after coating. A mixed gelatin and polyvinyl acetate subbing layer was then applied from a solution of the following composition:

Per cent Gelatin I 1.2 Water 10.0 Acetone 35.0 Methanol 53.8

' tent of this formula may be varied from 5-20% and the acetone content from 070% in which cases the balance of the solvent is methanol. Over the gelatin and polyvinyl acetate layer was then coated a silver halide emulsion layer.

Example 3 A film support oi cellulose acetate, 3ft-42% acetyl, was coated with a subbing solution of the following composition:

Per cent Gelatin 1.2 Acetone 69.0

Water 8.0 Methyl cellosolve 5.0 Methanol 15.8 Acetic acid 1.0

to which 2% of' the weight of gelatin of chromium chloride and lil-% of the weight of the gelatin of polyvinyl ,acetate had been added. The use of chromium chloride in gelatin subbing layers has been 4described in our prior Vapplication'Serial No. 295,268. Over the mixed gelatin and polyvinyl acetate layer was then coated a silver halide emulsion.

By an alternative method we have ilrst subbed a cellulose acetate base, 38-42% acetyl, with a mixed cellulose nitrate and polyvinyl acetate subbing layer from a solution such as described in Example 2 after which was applied a mixed gelatin and polyvinyl acetate subbing solution of the following composition Per cent Gelatin 1.2 Water 10.0 Methanol 87.8 Acetic acid 1.0

to which lil-30% of the weight oi' the gelatin of polyvinyl acetate wasadded. The water content of this formula may vary from 5-2y0% in which case the methanol content is varied accordingly. Over the gelatin and polyvinyl acetate layer was coated a sensitive emulsion layer.

Emample 4 40% of hydrolyzed cellulose acetate propionate,

10% propionyl and 29% acetyl in a manner simllar to that described in our prior application Serial No. 295,268 from a solution of the following composition Per cent Cellulose ester 2 Methyl cellosolve 25 Acetone 35 Methanol 33 Ethylene chloride 5 Over this sub layer was coater a layer of mixed gelatin and polyvinyl acetate rom a solution of the composition which follows:

to which was added 2% of the weight of the gela tin of chromium chloride and 1030% of the weight of the gelatin of polyvinyl acetate. Over this subbing layer ,was then coated an emulsion layer.

Example Per cent Gelatin 1.2 Water 10.0 Methanol 87.8 Acetic acid 1.0

to which was added 30% of the weight of the gelatin of polyvinyl acetate. The water content of this formula may vary from 5-20% in which case the amount of methanol is decreased. Over this subbing layer were coated several emulsion layers sensitized to record different regions of the spectrum. When this film was color processed it was found that no dye had been retained v in the subbing layers or the support.

We have referred to the use of our subbing method in film designed to receive color images. Film support may also be subbed according to our invention where the lm is designed to record black-and-white silver images. The color lms we describe may be designed to record sound as well as picture images and suitable light filtering layers may be positioned throughout the illm as is required. v

It is to be understood that the above examples, ranges and methods of procedure are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.

Having thus described our invention what we claim as new and wish to secure by Letters Pat. end of the United States is:

- 1. A photographic lm having low dye retention subbing layers, comprising a cellulose ester support, an emulsion layer adapted to receive a colored image, and between the emulsion and the support a subbing layer composed of a. mixture of gelatin and a polymeric material selected from the group consisting of polyvinyl organic acid esters, hydrolyzed polyvinyl organic acid esters, polyacrylic esters and polyvinyl acetals.

2. A photographiclm having low dye retention subbing layers, comprising a cellulose ester support, an emulsion layer adapted to receive a colored image and between the emulsion and the support; a subbing layer composed o1' a mixture of gelatin 'and a polyvinyl organic acid ester.

3. A photographic film for use in color photography having low dye retention subbing layers, comprising a cellulose organic acid ester support, an emulsion layer adapted to receive a colored image, and between the emulsion and Ithe support, a subbing layer composed of al mixture of gelatin and a polyvinyl organic acid ester.V

4. A photographicfllm for use in color photography having low dye retention vsubbing layers, comprising a cellulose acetate support, an emulsion layer adapted to receive a colored image, and between the emulsion and the support. :a subbing .layer composed of a mixtureof the gelatin and a polyvinyl organic acid ester. 5. A photographic nlm for use in color pho,

polyvinyl acetate.

tography having low dye retention subbing layers, comprising a cellulose acetate support, an emulsion layer adapted to receive a colored image, and between the emulsion and the support, a subbin'g layer composed of a mixture oi gelatin and polyvinyl acetate.

6. A photographic nlm for use in color photography having low dye retention subbing layers, comprising a cellulose mixed ester support, an

emulsion layer adapted to receivea colored image, and between the emulsion and the support, a subbing layer composed of a mixture of gelatin and a polyvinyl organic acid ester.

7. A photographic illm for use in color photography having low dye retention subbing layers, comprising a cellulosey acetate propionate support, an emulsion layer adapted to receive a colored image, andbetween .the emulsion and the support, a subbing layer composed of a mixture of gelatin and a polyvinyl organic acid ester.

8. A photographic film for use in color photography having low dye retention subbing layers, comprising a cellulose acetate propionate support, an emulsion layer adapted to receive a colored image, and between the emulsion and the support, a subbing layer composed oi a mixture of gelatin and polyvinyl acetate. v

9. A photographic illm for use in color photography having low dye retention subbing layers, comprising a cellulose inorganic acid ester support, an emulsion layer adapted to receive a colored image, and between the emulsionand the support, a subbing layer composed of a mixture of gelatin and a polyvinyl organic acid ester.

10. A photographic illm for use in color photography having 'low dye retention subbing layers. comprising a cellulose nitrate support. an emulsion layer adapted to receive a colored image, and between the emulsion and the support,l a subbing layer composed of a mixture of gelatin and a polyvinyl organic acid ester.

11. A photographic iilm for use in color photography having low dye retention subbing layers, comprising a cellulose nitrate support, an emulsion layer adapted to receive a colored image, y

and between the emulsion and the support, a subbing layer composed of a mixture .of gelatin and polyvinyl acetate.

l2. A photographic film for use in color phoemulsions and the support, a subbing layer comc posed of a mixture of gelatin and polyvinyl acetate.

14. A photographic lm for use in color photography having low dye retention subbing layers, comprising a cellulose acetate propionate support, a plurality of emulsion layers sensitized to record ,dinerent regions of the spectrum, andv betweenA thel emulsions and the support. a subbing layer composed of a mixture of gelatin and GLE F. NADEAU. CLEMENS B. ISTARGK. 

